105890-78-6Relevant articles and documents
N-heterocyclic carbene stabilized phosphaalkenyl(chloro)stannylene
Kocsor,Nemes,Saffon,Mallet-Ladeira,Madec,Castel,Escudie
, p. 2718 - 2721 (2014/02/14)
The new phosphaalkenyl(chloro)tin(ii) compound NHC-Sn(Cl)[C(SiMe 3)PMes*] was isolated and fully characterized including molecular structure determination by a single crystal X-ray diffraction analysis. Its reaction with Me2SAuCl led to the formation of an unprecedented PC-bridged trinuclear gold complex [AuC(SiMe3) PMes*]3 through the transfer of the phosphaalkenyl substituent to the gold atom.
Palladium( 0) mediated coupling of bromophosphaalkenes with Grignard reagents
Van Der Sluis, Marcel,Klootwijk, Angelique,Wit, Jan B.M.,Bickelhaupt, Friedrich,Veldman, Nora,Spek, Anthony L.,Jolly, Peter W.
, p. 107 - 119 (2007/10/03)
Attempts to subject the phosphaalkene Mes * P = CBr2 (1) (Mes * = supermesityl = 2,4,6-tri-tert-butylphenyl) to a palladium(0) catalyzed Stille-type coupling reaction with phenylmagnesium chloride failed due to elimination of palladium bromide and rearrangement to the phosphaacetylene Mes * C≡P (2). To prevent this undesired reaction, the monobromophosphaalkene Mes * P=C(H)Br (6) was used. Although both isomers are known, a new method for the synthesis of (E)-Mes * P=C(H)Br ((E)-6) has been developed and the compound tested in Stille-type coupling reactions with organometallic reagents. Best results were obtained in combination with Grignard reagents; aromatic, olefinic and alkynyl groups could be introduced. Most unexpected was the result when (Z)-Mes * P=C(Br)H ((Z)-6) was subjected to this coupling reaction: in all cases, isomerization occurred to give (E)-Mes * P=C(H)R (7-17) in high yield and purity. This method offers a convenient access to a variety of new functionalized phosphaalkenes with potentially interesting coordinating properties. The mechanism of the coupling reaction appears not to involve the usual oxidative addition step, assumed to occur in the normal Stille coupling. Attempts to elucidate the mechanism are reported and the η2-palladium complex 19 has been tentatively identified as an intermediate.
SYNTHESIS AND REACTIVITY OF P-SUPERMESITYL-C-HALOPHOSPHAALKENES
Goede, Simon J.,Schaik, Henk P. van,Bickelhaupt, Friedrich
, p. 252 (2007/10/02)
The synthesis of the title compounds in high yield via a new route are presented and their reaction with n-butyllithium and subsequent functionalisations is discussed.
Synthesis and Reactions of P-Supermesityl-C-halophosphaalkenes
Goede, Simon J.,Bickelhaupt, Friedrich
, p. 2677 - 2684 (2007/10/02)
C-Halophosphaalkenes (1, 2) were prepared in high yield by a one-pot synthesis from HCX3 or CI4 and Mes*PCl2 (Mes* = supermesityl = 2,4,6-tri-tert-butylphenyl).The C-iodophosphoaalkenes Mes*P=Cl2 (1c) and Mes*P=CHI (2c) undergo halogen-metal exchange with n-BuLi at low temperatures.The resulting carbenoids Mes*P=CILi (11c) and Mes*P=CHLi (6) reacted with ClMMe3 (M = Si, Ge, Sn) to give Mes*P=CIMMe3 or Mes*P=CHMMe3 (8-10), respectively.Further reaction of (Z)-13 and (Z)-14 with n-BuLi and ClMMe3 gave Mes*P=C(MMe3)2 (18: M = Ge; 19: M = Sn).The carbenoid (Z)-11c decomposed at -85 deg C; instead of the expected "phosphaisonitrile" Mes*P=C: (21), only Mes*CP (15) was obtained which lends experimental support to the theoretically predicted instability of 21.Key Words: Phosphaalkenes, C-halo, C-metal / "Phospha-isonitrile" / Phosphinylidenemethylene / Phosphaalkyne, E/Z isomers
